Research into a gas sensing material with excellent performance to detect or remove toxic phosgene (COCl₂) is of great significance to environmental and biological protection. In the present work, the adsorption performance of COCl₂ on pristine phthalocyanine (Pc) and metal-decorated Pc (MePc, Me = Cu, Ga, and Ru) monolayers was studied by first-principles calculations. The results show that the absorption process of COCl₂ on pristine Pc and CuPc both belong to physisorption, indicating that they are not suitable gas sensing materials for COCl₂. When Pc sheets are decorated by Ga and Ru atoms, the adsorption of COCl₂ is changed into chemisorption, and the corresponding adsorption energies are -0.57 and -0.50 eV for GaPc and RuPc, respectively. The microcosmic mechanism between COCl₂ and adsorbents (GaPc, RuPc) was clarified by the analysis of the density of states, the charge density difference, and the Hirshfeld charge. In addition, the COCl₂ adsorption results in a significant conductivity variation of the RuPc monolayer, demonstrating it exhibits a high sensitivity to the COCl₂ molecule. Meanwhile, quick desorption processes were noticed at various temperatures for the COCl₂/RuPc system. Consequently, the RuPc monolayer can be considered as a potential candidate for phosgene sensors because of the moderate adsorption strength, high sensitivity, and fast desorption speed.